Production of polycrystalline silicon in substantially closed-loop systems

ABSTRACT

Production of polycrystalline silicon in a substantially closed-loop process is disclosed. The processes generally include decomposition of trichlorosilane produced from metallurgical grade silicon.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation of U.S. patent Ser. No. 12/910,540,filed Oct. 22, 2010 and is a continuation of U.S. patent Ser. No.12/910,553, filed Oct. 22, 2010, both of which are incorporated hereinby reference.

BACKGROUND

The field of the present disclosure relates to production ofpolycrystalline silicon in a substantially closed-loop process and,particularly, processes that include decomposition of trichlorosilaneproduced from metallurgical grade silicon.

Polycrystalline silicon is a vital raw material used to produce manycommercial products including, for example, integrated circuits andphotovoltaic (i.e., solar) cells. Polycrystalline silicon is oftenproduced by a chemical vapor deposition mechanism in which silicon isdeposited from a thermally decomposable silicon compound onto siliconparticles in a fluidized bed reactor or onto silicon rods as in aSiemens-type reactor. The seed particles continuously grow in size untilthey exit the reactor as polycrystalline silicon product (i.e.,“granular” polycrystalline silicon). Suitable decomposable siliconcompounds include, for example, silane and halosilanes such astrichlorosilane.

Trichlorosilane may be produced by contacting hydrogen chloride with asource of silicon as shown in the reaction below,

Si+3HCl→SiHCl₃+H₂   (1),

or by contacting silicon tetrachloride and hydrogen with a source ofsilicon as shown in the reaction below,

Si+3SiCl₄+2H₂→4SiHCl₃   (2).

Hydrogen chloride and silicon tetrachloride are relatively expensivecomponents in trichlorosilane-based production of polycrystallinesilicon.

A continuing need exists for processes for producing polycrystallinesilicon by thermal decomposition of trichlorosilane that reduce theamount of hydrogen and chlorine used relative to conventional methodsand for methods that are capable of producing polycrystalline silicon ina substantially closed-loop process relative to hydrogen chloride. Acontinuing need also exists for systems for producing polycrystallinesilicon that make use of such processes.

SUMMARY

One aspect of the present disclosure is directed to a system forproducing polycrystalline silicon by decomposition of trichlorosilane.The system is substantially closed-loop with respect to trichlorosilane.The system includes a chlorination reactor in which hydrogen chloride iscontacted with silicon to produce trichlorosilane and silicontetrachloride. The system includes a fluidized bed reactor in whichtrichlorosilane is decomposed to produce polycrystalline silicon. Thesystem also includes a hydrogenation reactor in which silicontetrachloride and hydrogen are introduced to produce trichlorosilane.

Another aspect of the present disclosure is directed to a system forproducing polycrystalline silicon by decomposition of trichlorosilane.The system is substantially closed-loop with respect to trichlorosilane.The system includes a chlorination reactor in which hydrogen chloride iscontacted with silicon to produce trichlorosilane and silicontetrachloride. The system includes a first fluidized bed reactor inwhich trichlorosilane is decomposed to produce polycrystalline silicon.The system includes a second fluidized bed reactor in which silicontetrachloride is contacted with hydrogen and particulate silicon toproduce trichlorosilane.

Various refinements exist of the features noted in relation to theabove-mentioned aspects of the present disclosure. Further features mayalso be incorporated in the above-mentioned aspects of the presentdisclosure as well. These refinements and additional features may existindividually or in any combination. For instance, various featuresdiscussed below in relation to any of the illustrated embodiments of thepresent disclosure may be incorporated into any of the above-describedaspects of the present disclosure, alone or in any combination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow diagram of a system for producing polycrystallinesilicon by the thermal decomposition of trichlorosilane according to afirst embodiment of the present disclosure;

FIG. 2 is a flow diagram of a system for producing polycrystallinesilicon by the thermal decomposition of trichlorosilane according to asecond embodiment of the present disclosure;

FIG. 3 is a flow diagram of a purification system for purifying aneffluent gas containing trichlorosilane and silicon tetrachlorideaccording to a first embodiment of the present disclosure;

FIG. 4 is a flow diagram of a separation system for separating andpurifying hydrogen and hydrogen chloride according to a first embodimentof the present disclosure; and

FIG. 5 is a flow diagram of a second effluent gas separation system forpurifying a second effluent gas discharged from a second fluidized bedreactor for hydrogenating silicon tetrachloride.

Corresponding reference characters indicate corresponding partsthroughout the drawings.

DETAILED DESCRIPTION

In accordance with the present disclosure, substantially closed-loopprocesses and systems for producing polycrystalline silicon fromtrichlorosilane are provided. As used herein, the phrases “substantiallyclosed-loop process” or “substantially closed-loop system” refers to aprocess or system in which the compound with respect to which the systemor process is substantially closed-loop is not withdrawn into the systemor process other than as an impurity and is not fed into the system orprocess other than as in a make-up stream. As used herein, the systemsand processes are substantially closed-loop with respect to allcompounds other than silicon such as, for example, trichlorosilane,silicon tetrachloride, hydrogen chloride and/or hydrogen.

Closed-loop Processes for Producing Polycrystalline Silicon

In several embodiments of the present disclosure and as shown in FIG. 1,a source of silicon 3 and hydrogen chloride 6 are introduced andcontacted in a chlorination reactor 7 to produce a chlorinated productgas 10. The chlorinated product gas 10 contains trichlorosilane andsilicon tetrachloride as well as hydrogen and unreacted hydrogenchloride. Trichlorosilane and silicon tetrachloride may be produced inthe chlorination reactor 7 according to the following reactions,

Si+3HCl→SiHCl₃+H₂   (3),

SiHCl₃+HCl→SiCl₄+H₂   (4).

In this regard it should be understood that, as used herein, “contact”of two or more reactive compounds generally results in a reaction of thecomponents and the terms “contacting” and “reacting” are synonymous asare derivations of these terms and these terms and their derivationsshould not be considered in a limiting sense. Typically the source ofsilicon 3 is metallurgical grade silicon; however, it should beunderstood that other sources of silicon may be used such as, forexample, sand (i.e., SiO₂), quartz, flint, diatomite, mineral silicates,fluorosilicates and mixtures thereof. It is preferred that the particlesize of the silicon be from about 10 μm to about 750 μm or from about 50μm to about 250 μm. Increasing the particle size decreases the reactionrate while smaller sizes result in more particles being entrained inspent reactor gases and difficulty in fluidization as a result ofincreased cohesive forces among the smaller diameter particles.

The chlorination reactor 7 may be a fluidized bed reactor in whichsilicon 3 is suspended in the incoming hydrogen chloride gas 6. Thereactor 7 may be operated at a temperature of at least about 250° C.and, in other embodiments, at least about 300° C. (e.g., from about 250°C. to about 450° C. or from about 300° C. to about 400° C.). In view ofthe exothermic nature of reactions (3) and (4), the chlorination reactor7 may include cooling means (e.g., cooling coils in thermalcommunication with the reactor bed or a cooling jacket) to assist incontrolling the temperature of the reactor. In this regard, it should beunderstood that while the chlorination reactor 7 may be a fluidized bedreactor, it should be understood that, as used herein, the chlorinationreactor should be distinguished from the “first fluidized bed reactor”and the “second fluidized bed reactor” described below.

The reactor 7 may be operated at a pressure (i.e., overhead gaspressure) of at least about 1 bar such as, for example, from about 1 barto about 10 bar, from about 1 bar to about 7 bar or from about 2 bar toabout 5 bar. The incoming hydrogen chloride stream 6 may include anamount of impurities such as chlorosilanes (e.g., silicon tetrachlorideand/or trichlorosilane). In various embodiments of the presentdisclosure, the hydrogen chloride stream 6 comprises at least about 80vol % hydrogen chloride, at least about 90 vol %, at least about 95 vol% or even at least about 99 vol % hydrogen chloride (e.g., from about 80vol % to about 99 vol % or from about 90 vol % to about 99 vol %).

The chlorination reactor 7 may include an amount of catalyst to promoteformation of trichlorosilane relative to formation of silicontetrachloride in the chlorinated product gas 10. For instance, thechlorination reactor 7 may include a group VIII metal catalyst (e.g.,iron, cobalt, nickel, vanadium and/or platinum) or a catalyst containingaluminum, copper or titanium metal as disclosed in U.S. Pat. No.5,871,705, which is incorporated herein by reference for all relevantand consistent purposes. The reactor 7 may also include an amount of oneor more alkali metal compounds (e.g., lithium chloride, sodium chloride,potassium chloride, cesium chloride, rubidium chloride, sodium sulfateand/or sodium nitrate) to increase the selectivity towardtrichlorosilane. The reactor 7 may be operated at from about 1.1 timesto about 8 times the minimum fluidization velocity or from about 1.5 toabout 4 times the minimum fluidization velocity.

The conversion of hydrogen chloride in the chlorination reactor 7 mayvary depending on the reaction conditions and, typically, will be atleast about 50%, at least about 65%, at least about 80%, at least about90% and in some embodiments, conversion may approach 100% (e.g., fromabout 50% to about 100% or from about 80% to about 100%). Selectivitytoward trichlorosilane may be at least about 50%, at least about 65% oreven at least about 80% (e.g., from about 50% to about 90% or from about70% to about 90%).

The chlorinated product gas 10 is introduced into a purification system4 to produce a purified trichlorosilane stream 20 and a purified silicontetrachloride stream 22. The purification system 4 may also separatehydrogen and hydrogen chloride 26 from the purified trichlorosilane 20and purified silicon tetrachloride 22 and may separate various metalimpurities (e.g., metal chlorides) from the gas streams 20, 22. Thetrichlorosilane stream 20 may be purified to contain less than about 10vol % of compounds other than trichlorosilane (e.g., silicontetrachloride) and preferably contains less amounts of impurities suchas, less than about 5 vol %, less than about 1 vol %, less than about0.1 vol % or even less than about 0.001 vol % of compounds other thantrichlorosilane. Typically, the purified silicon tetrachloride stream 22contains at least about 50 wt % silicon tetrachloride and, in someembodiments, at least about 60 wt %, at least about 70 wt %, at leastabout 80 wt % or even at least about 90 wt % silicon tetrachloride. Inthis regard, it should be understood that it is acceptable for thesilicon tetrachloride stream 22 to be relatively impure (e.g., for thepurity to be as low as 50 wt % or even lower) as the silicontetrachloride stream is further processed to form trichlorosilane asdescribed below.

The purified trichlorosilane stream 20 is introduced into the fluidizedbed reactor 30 in which it fluidizes growing silicon seed particles toproduce polycrystalline silicon which may be withdrawn from the reactor30 as polycrystalline silicon product 27. Polycrystalline silicon 27 isproduced from trichlorosilane 20 with formation of silicon tetrachlorideby-product according to the following reactions,

SiHCl₃+H₂→Si+3HCl   (5),

SiHCl₃+HCl→SiCl₄+H₂   (6).

In addition to trichlorosilane 20, hydrogen 29 is introduced into thefluidized bed reactor 30 as a carrier gas and to improve the overallconversion to polycrystalline silicon 27. The fluidized bed reactor 30may be operated in accordance with U.S. application Ser. No. 12/910,465, filed Oct. 22, 2010, published as U.S. Pat. Pub. No. ______,which isincorporated herein by reference for all relevant and consistentpurposes. For instance, trichlorosilane 20 may be directed to the coreregion of the reactor 30 and the overall concentration oftrichlorosilane introduced into the reactor may be at least about 20% byvolume (e.g., from about 20% to about 50% by volume). Incoming feedgases may be at a temperature of less than about 350° C. The reactor 30may be operated at less than about 90% equilibrium and with a residencetime of less than about 10 seconds. The reactor 30 may be operated at apressure of from about 3 bar to about 8 bar and the reaction gases maybe heated to a temperature of at least about 700° C. (e.g., from about700° C. to about 1300° C.). The gas velocity through the fluidized bedreactor 30 may be generally maintained at a velocity of from about 1 toabout 8 times the minimum fluidization velocity necessary to fluidizethe particles within the fluidized bed. The mean diameter of theparticulate polycrystalline silicon that is withdrawn from the reactor30 may be from about 800 μm to about 1200 μm. Quench gases may beintroduced into the reactor 30 (e.g., at a freeboard region of thereactor) to reduce the temperature of the effluent gas 32 before beingdischarged from the reactor to suppress formation of silicon dust. Thefluidized bed reactor may include an outer shell in which an inert gasis maintained at a pressure above the pressure of the process gases(e.g., a pressure within the range of about 0.005 bar to about 0.2 bar)to ensure process gases do not flow through cracks and holes within thereaction chamber.

In some embodiments of the present disclosure, the conversion oftrichlorosilane in the fluidized bed reactor may be at least about 40%,at least about 55%, at least about 70% or even at least about 80% (e.g.,from about 40% to about 90% or from about 55% to about 90%). Theselectivity toward deposited silicon may be at least about 10%, at leastabout 15%, at least about 20%, at least about 25% or even at least about30% (e.g., from about 15% to about 40% or from about 20% to about 30%).

The effluent gas 32 that exits the reactor 30 includes silicontetrachloride, unreacted trichlorosilane and hydrogen. The effluent gas32 may also contain minor amounts of other gases (e.g., hydrogenchloride) and silicon dust. In some embodiments of the presentdisclosure, the effluent gas 32 may contain at least about 10 vol %silicon tetrachloride, at least about 15 vol %, at least about 20 vol %or at least about 30 vol % silicon tetrachloride (e.g., from about 10vol % to about 40 vol % or from about 10 vol % to about 20 vol % silicontetrachloride). The effluent gas 32 may include at least about 10 vol %unreacted trichlorosilane, at least about 15 vol %, at least about 20vol % or at least about 30 vol % unreacted trichlorosilane (e.g., fromabout 10 vol % to about 40 vol % or from about 10 vol % to about 20 vol% unreacted trichlorosilane). The bulk of the remainder of the effluentgas is typically hydrogen. For instance, the effluent gas 32 that exitsthe fluidized bed reactor 30 may include at least about 40 vol %hydrogen, at least about 50 vol %, at least about 60 vol %, at leastabout 70 vol %, at least about 80 vol % or even at least about 90 vol %hydrogen (e.g., from about 40 vol % to about 90 vol % or from about 60vol % to about 80 vol%). The amount of hydrogen chloride in the effluentgas 32 may be less than about 5 vol % and is typically less than about 1vol % (e.g., from about 0.1 vol % to about 5 vol %). The amount ofsilicon dust in the effluent gas may be from about 0.1 wt % to about 5wt %. In this regard, it should be understood that the above-referencedpercentage inclusion for the recited components are exemplary and otherrelative amounts of components may be used without departing from thescope of the present disclosure.

The effluent gas 32 is introduced into an effluent gas separator 50 toseparate hydrogen (and hydrogen chloride if present) 31 from silicontetrachloride and unreacted trichlorosilane 36. Before introduction intothe effluent gas separator 50, the gas may pass through a particulateseparator (not shown) to remove silicon dust produced as a by-product ofthe thermal decomposition of trichlorosilane. The separated silicontetrachloride and trichlorosilane 36 may be recycled back to thepurification system 4 for further use. The hydrogen (and any hydrogenchloride) 31 is introduced into a separation system 52 to separatehydrogen 54 and hydrogen chloride 6 which is more fully described below.

The separator 50 may be constructed according to any of the methods forseparating gaseous components as appreciated by those of skill in theart. In some embodiments, the separator 50 is a vapor-liquid separator.Examples of such vapor-liquid separators include vessels in which thepressure and/or temperature of the incoming gas is reduced causing thelower boiling-point gases (e.g., silicon tetrachloride andtrichlorosilane) to condense and separate from higher boiling pointgases (e.g., hydrogen and hydrogen chloride). Suitable vessels includevessels which are commonly referred to in the art as “knock-out drums.”Optionally, the vessel may be cooled to promote separation of gases.Alternatively, the separator 50 may be one or more distillation columns.

Silicon tetrachloride 22 removed from the purification system 4 isintroduced into a hydrogenation reactor 60 to produce trichlorosilane.Silicon tetrachloride 22 discharged from the purification system 4includes silicon tetrachloride that is produced as a by-product in thechlorination reactor 7 and as a by-product in the polycrystallinesilicon fluidized bed reactor 30. In addition to silicon tetrachloride22, hydrogen 57 from the separation system 52 is introduced into thehydrogenation reactor 60. Silicon tetrachloride 4 that is removed fromthe purification system 22 is converted to trichlorosilane according tothe following reaction,

SiCl₄+H₂→SiHCl₃+HCl   (7).

The hydrogenation reactor 60 may be a bubbler in which hydrogen 57 isbubbled through liquid silicon tetrachloride 22 to form trichlorosilane.Alternatively, silicon tetrachloride 22 is vaporized and the hydrogen 57and silicon tetrachloride 22 are heated and reacted in a pressurizedreaction vessel. In this regard, any vessel suitable for thehydrogenation reaction as appreciated by those of skill in the art maybe used without limitation. The contents of the reaction vessel may beheated to a temperature of at least about 800° C. to convert silicontetrachloride to trichlorosilane. In some embodiments, silicontetrachloride 22 and hydrogen 57 are heated to a temperature of at leastabout 900° C., at least about 1000° C. or even at least about 1100° C.(e.g., from about 800° C. to about 1500° C., from about 800° C. to about1200° C. or from about 1000° C. to about 1200° C.). Preferably, thereaction vessel is pressurized to promote formation of trichlorosilane.For instance, the hydrogenation reactor 60 may be operated at a pressureof at least about 2 bar and, in other embodiments, at least about 5 bar,at least about 10 bar or even at least about 15 bar (e.g., from about 2bar to about 20 bar or from about 8 bar to about 15 bar). The ratio ofhydrogen to silicon tetrachloride introduced into the rector 60 may varydepending on the reaction conditions. Use of a stoichiometric excess ofhydrogen typically results in increased conversion to trichlorosilane.In various embodiments, the molar ratio of hydrogen to silicontetrachloride is at least about 1:1, at least about 2:1 or even at leastabout 3:1 (e.g., from about 1:1 to about 5:1 or from about 1:1 to about3:1).

Generally, at least about 20% of silicon tetrachloride is converted totrichlorosilane in the hydrogenation reactor 60 with conversions of atleast about 30%, at least about 40% or even at least about 50% beingpossible (e.g., from about 20% to about 60% conversion). The resultinghydrogenated gas 63 contains trichlorosilane, unreacted silicontetrachloride, unreacted hydrogen and hydrogen chloride. Depending onthe amount of excess hydrogen 57 added to the reactor, the amount oftrichlorosilane in the hydrogenated gas 63 may be at least about 5 vol %and, in other embodiments, at least about 10 vol %, at least about 25vol %, or at least about 40 vol % (e.g., from about 5 vol % to about 40vol %, from about 5 vol % to about 20 vol % or from about 5 vol % toabout 10 vol %). Likewise, the amount of hydrogen chloride in thehydrogenated gas may be at least about 5 vol % and, in otherembodiments, at least about 10 vol %, at least about 25 vol %, or atleast about 40 vol % (e.g., from about 5 vol % to about 40 vol %, fromabout 5 vol % to about 20 vol % or from about 5 vol % to about 10 vol%). The amount of unreacted silicon tetrachloride may be at least about10 vol %, at least about 20 vol %, or at least about 30 vol % or atleast about 40 vol % of the hydrogenated gas stream (e.g., from about 10vol % to about 40 vol %, from about 10 vol % to about 30 vol % or fromabout 15 vol % to about 25 vol %). The remainder of the hydrogenated gas63 is typically hydrogen. For instance, the hydrogenated gas 63 mayinclude at least about 40 vol % hydrogen or, as in other embodiments, atleast about 50 vol %, at least about 60 vol %, at least about 70 vol %or even at least about 80 vol % hydrogen (e.g., from about 40 vol % toabout 90 vol %, from about 50 vol % to about 80 vol % or from about 60vol % to about 80 vol %).

The hydrogenated gas 63 is introduced into a hydrogenated gas separator70 to separate trichlorosilane and unreacted silicon tetrachloride 73from hydrogen and unreacted hydrogen chloride 75. The trichlorosilaneand unreacted silicon tetrachloride 73 are introduced into the gaspurification system 4 to recover trichlorosilane 20 and to reintroducesilicon tetrachloride 73 to the hydrogenation reactor 60. Separatedhydrogen and hydrogen chloride 75 are introduced into the separationsystem 52 described below. The hydrogenated gas separator 70 may be avapor-liquid separator such as a knock-out drum or may be a distillationcolumn as described above with reference to the separator 50.

The separation system 52 separates hydrogen 54 from hydrogen chloride 6.Hydrogen 54 may be used in the hydrogenation reactor 60 and/or thefluidized bed reactor 30. Hydrogen chloride 6 is used in thechlorination reactor 7. Hydrogen and hydrogen chloride steams that areintroduced into the separation system 52 include hydrogen and/orhydrogen chloride 26 from the purification system 4, hydrogen and/orhydrogen chloride 31 from the separator 50 and hydrogen and/or hydrogenchloride from the hydrogenated gas separator 70.

An alternative embodiment for producing polycrystalline silicon is shownin FIG. 2. In this regard, it should be noted that the process steamsand apparatus shown in FIG. 2 that are analogous to those of FIG. 1 aredesignated by the corresponding reference number of FIG. 1 plus “100”(e.g., part 4 becomes part 104). The process of FIG. 2 is substantiallythe same as that of FIG. 1; however, FIG. 2 includes a second fluidizedbed reactor 180 rather than a hydrogenation reactor 60 (FIG. 1). In thisregard, it should be understood that in certain embodiments, the processmay use both a hydrogenation reactor 60 (FIG. 1) and a second fluidizedbed reactor 180 (FIG. 2) operated in series or parallel withoutdeparting from the scope of the present disclosure.

In the process of FIG. 2, silicon tetrachloride 122 removed from thepurification system 104 is introduced into the second fluidized bedreactor 180. Hydrogen 157 from the separation system 152 is introducedinto the fluidized bed reactor 180 as a carrier gas. A source of silicon185 is also introduced into the second fluidized bed reactor 180. Theparticulate silicon 185 is fluidized by the hydrogen 157 and silicontetrachloride gas 122 introduced into the reactor 180. Introduction of asource of silicon into the fluidized bed reactor 180 allows silicontetrachloride to be directly hydrogenated to produce trichlorosilaneaccording to the following reaction,

3SiCl₄+2H₂+Si->4SiHCl₃   (8).

The direct hydrogenation reaction (8) may be performed in accordancewith known operating parameters such as those described in U.S. Pat. No.4,526,769 or U.S. Pat. No. 4,676,967, both of which are incorporatedherein by reference for all relevant and consistent purposes. Thefluidized bed reactor 180 may be operated at a temperature of at leastabout 500° C. and, in some embodiments, at least about 550° C., at leastabout 600° C., at least about 650° C. or at least about 700° C. (e.g.,from about 500° C. to about 750° C. or from about 550° C. to about 650°C.). Silicon tetrachloride 122 and/or hydrogen 157 may be preheatedprior to the introduction into the fluidized bed reactor 180 and/or heatmay extraneously be added to the reactor 180 by use of external heatingmeans. The fluidized bed reactor 180 may be operated at an elevatedpressure such as pressures of at least about 3 bar or at least about 6bar; however, relatively high pressures such as at least about 20 bar,at least about 25 bar, at least about 30 bar or at least about 35 bar(e.g., from about 20 bar to about 35 bar) may be used to minimizecorrosion and increase trichlorosilane yield.

The source of silicon 185 may be metallurgical grade silicon; however,it should be understood that other sources of silicon may be used suchas, for example, sand (i.e., SiO₂), quartz, flint, diatomite, mineralsilicates, fluorosilicates and mixtures thereof. The particle size ofthe silicon may be from about 10 μm to about 500 μm or from about 50 μmto about 300 μm. Silicon 185, silicon tetrachloride 122 and hydrogen 157may be added in substantially equimolar amounts; however, hydrogen maybe used as a carrier gas and may be added in a stoichiometric excess.The molar ratio of hydrogen to silicon tetrachloride may be at leastabout 2:3, at least about 1:1, at least about 2:1, at least about 3:1 orat least about 5:1 (e.g., from about 2:3 to about 5:1).

In some embodiments of the present disclosure, a catalyst may be addedto the fluidized bed reactor 180 to achieve higher conversion totrichlorosilane. In some embodiments, a copper-containing catalyst maybe added to the second fluidized bed reactor 180. Examples of such acatalyst include copper oxides and copper chlorides such as, forexample, CuO, Cu₂O, CuCl and CuCl₂. Regardless of whether a catalyst isemployed, at least about 20% of silicon tetrachloride is converted totrichlorosilane in the second fluidized bed reactor 180 with conversionsof at least about 30%, at least about 40% or even at least about 50%being possible (e.g., from about 20% to about 60% conversion).

As shown in FIG. 2, the second effluent gas 164 from the secondfluidized bed reactor 180 is introduced into a second effluent gasseparation system 190. The second effluent gas 164 includestrichlorosilane, unreacted silicon tetrachloride, unreacted hydrogen andmay contain other compounds such as hydrogen chloride anddichlorosilane. In several embodiments of the present disclosure, asystem 190 as shown in FIG. 5 may be used. The system 190 includes aparticulate separator 192 that removes silicon particulate (e.g., dust)193 that is carried out of the second fluidized bed reactor 180.Suitable particulate separators include, for example, bag filters,cyclonic separators and liquid scrubbers. Silicon dust 193 may berecycled back to the second fluidized bed reactor 180 for furtherconversion to trichlorosilane. The dust-depleted effluent gas 194 isintroduced into a separator 195. The separator 195 may be a vapor-liquidseparator as described above (e.g., knock-out drum) with reference toseparator 50 (FIG. 1) or may be a distillation column. The separator 195separates trichlorosilane and unreacted silicon tetrachloride 173 fromhydrogen and hydrogen chloride (if any) 175. The trichlorosilane andreacted silicon tetrachloride 173 are introduced into the gaspurification system 104 (FIG. 2) to recover trichlorosilane 120 andreintroduce silicon tetrachloride 122 to the second fluidized bedreactor 180. Separated hydrogen and hydrogen chloride 175 are introducedinto the separation system 152.

An exemplary purification system 4 for use in embodiments of the presentdisclosure is shown in FIG. 3. In this regard, it should be understoodthat the purification system 104 (FIG. 2) may be the same or similar tothe purification system 4 shown in FIG. 3 without departing from thescope of the present disclosure. The purification system 4 includes aparticulate separator 11 that removes silicon dust 13 formed duringdecomposition of trichlorosilane from the chlorinated product gas 10.Suitable particulate separators include, for example, sintered metalfilters, bag filters, cyclonic separators and liquid scrubbers. Silicondust 13 may be withdrawn as waste or may be recycled to the firstfluidized bed reactor 30. Dust-depleted chlorinated product gas 19 isintroduced into a chlorinated gas separator 16 to separatetrichlorosilane and silicon tetrachloride 12 from hydrogen and unreactedhydrogen chloride 26. The chlorinated gas separator 16 may be avapor-liquid separator as described above (e.g., knock-out drum) withreference to separator 50 (FIG. 1) or may be a distillation column. Thehydrogen and unreacted hydrogen chloride 26 are introduced into theseparation system 52 (FIG. 1) to separate hydrogen and hydrogenchloride. The separated trichlorosilane and silicon tetrachloride 12 areintroduced into a silicon tetrachloride separator 18 to separate silicontetrachloride 22 from trichlorosilane and produce a trichlorosilane feedgas 17. The silicon tetrachloride separator 18 may be a distillationcolumn or any other apparatus suitable to remove silicon tetrachloridefrom trichlorosilane. The trichlorosilane feed gas 17 is introduced intoa trichlorosilane purifier 15 to remove impurities from the feed gas.The purifier 15 may also be a distillation column or any other apparatussuitable to remove impurities 14 from trichlorosilane-containing gases.The impurities 14 may be removed as waste or may be recycled (such as byintroduction into the separator system 52). The purified trichlorosilanefeed gas 20 is introduced into the fluidized bed reactor 30 (FIG. 1) toproduce polycrystalline silicon 27.

An embodiment of the separator system 52 is shown in FIG. 4. In thisregard, it should be understood that the separator system 152 (FIG. 2)may be the same or similar to the separator system 52 shown in FIG. 4.Hydrogen and hydrogen chloride 26 from the purification system 4,hydrogen and hydrogen chloride 31 from the separator 50 and hydrogen andhydrogen chloride 75 from the hydrogenated gas separator 70 areintroduced into a hydrogen separator 42 to produce a hydrogen recyclegas 45 and a hydrogen chloride recycle gas 47. In this regard, it shouldbe understood that one or more of the hydrogen and hydrogen chloridegases 26, 31, 75 may be first introduced into a purifier (not shown)such as a distillation column for purifying the hydrogen and hydrogenchloride (e.g., by removing any chlorides such as silicon tetrachloride,trichlorosilane and/or dichlorosilane) prior to introduction into thehydrogen separator 42. In embodiments wherein such a purifier is used,the chlorides may be recycled to the purification system 4.

The hydrogen recycle gas 45 is introduced into a hydrogen purifier 49 toremove impurities 41 from the hydrogen recycle gas 45. The impurities 41may be removed from the system as waste or may be recycled (e.g.,introduced into the purification system 4). The purified hydrogenrecycle gas 54 is introduced into the fluidized bed reactor 30 orhydrogenation reactor 60 (FIG. 1) or the second fluidized bed reactor180 (FIG. 2). The hydrogen chloride recycle gas 47 is introduced into ahydrogen chloride purifier 44 to remove impurities 42 from the hydrogenchloride recycle gas 47. The impurities 42 (e.g., chlorosilanes) may beremoved from the system as waste or may be recycled (e.g., introducedinto the purification system 4). The purified hydrogen chloride recyclegas 6 is recycled to the chlorination reactor 7.

The hydrogen separator 42 may be any type of separator suitable toseparate hydrogen from hydrogen chloride. An exemplary separator 42 is abubbler in which hydrogen and hydrogen chloride are bubbled through avessel containing a fluid (e.g., water) and, typically, in which thefluid is continuously introduced (not shown) and removed. Hydrogenchloride is adsorbed within the fluid (e.g., water) while separatedhydrogen is removed from the vessel as a gas. Hydrogen 45 is sent to thehydrogen purifier 49 which may be an adsorber or any other apparatussuitable for removing impurities from hydrogen gases. The hydrogenchloride purifier 44 may be one or more distillation columns. In thisregard, it should be understood that other methods and apparatus forseparating and purifying hydrogen and hydrogen chloride other than thoserecited above may be used in any combination (e.g., in series or inparallel) without departing from the scope of the present disclosure.

In several embodiments of the present disclosure, the molar ratio ofchlorine (i.e., based on the moles of chlorine atoms (Cl) rather thanmoles of the diatomic gas (Cl₂)) added as a make-up, including chlorinegas itself and chlorine atoms that form part of otherchlorine-containing compounds (e.g., HCl, SiHCl₃ and/or SiCl₄) that areadded in a make-up stream, to polycrystalline silicon product that isproduced (not including silicon dust) is less than about 2:1 and, as inother embodiments, less than about 1:1, less than about 1:1.2, less thanabout 1:1.5, less than about 1:2 or less than about 1:2.5 (e.g., fromabout 2:1 to 1:5 or from about 1:1 to about 1:5). In addition oralternatively, the molar ratio of hydrogen (i.e., based on the moles ofhydrogen atoms (H) rather than moles the diatomic gas (H₂)) added as amake-up, including hydrogen gas itself and hydrogen atoms that form partof other hydrogen-containing compounds (e.g., HCl, SiHCl₃, SiCl₄ and/orSiH₄) that are added in a make-up stream (but excluding hydrogenincluded within water that is used to separate hydrogen from hydrogenchloride in a bubbler-type system), may be less than about 1:1 and, asin other embodiments, less than about 1:2, less than about 1:3, lessthan about 1:5, less than about 1:10 (e.g., from about 1:1 to 1:20 orfrom about 1:2 to about 1:10). In some embodiments, no hydrogen is addedto the process as a make-up stream. Additionally, in some embodiments,no trichlorosilane or silicon tetrachloride are added to the system;rather, these compounds are produced and consumed within the systemitself.

Closed-loop Systems for Producing Polycrystalline Silicon

The processes described above may be incorporated into a substantiallyclosed-loop system for producing polycrystalline silicon. The processesabove may be substantially closed-loop with respect to trichlorosilane,hydrogen and/or hydrogen chloride. In several embodiments of the presentdisclosure and as shown in FIG. 1, the system includes a chlorinationreactor 7 in which hydrogen chloride is contacted with silicon toproduce trichlorosilane and silicon tetrachloride. The system alsoincludes a fluidized bed reactor 30 in which trichlorosilane isdecomposed to produce polycrystalline silicon and a hydrogenationreactor 60 in which silicon tetrachloride and hydrogen are introduced toproduce trichlorosilane. The system may include a conveying apparatusfor conveying trichlorosilane from the hydrogenation reactor 60 to thefluidized bed reactor 30 and a conveying apparatus for conveyingtrichlorosilane from the chlorination reactor 7 to the fluidized bedreactor 30.

The system may also include a purification system 4 to whichtrichlorosilane and silicon tetrachloride are introduced to separatetrichlorosilane and silicon tetrachloride. The system includes aconveying apparatus for conveying trichlorosilane from the purificationsystem 4 to the fluidized bed reactor 30 and a conveying apparatus forconveying silicon tetrachloride from the purification system 4 to thehydrogenation reactor 60. With further reference to FIG. 1, the systemmay include an effluent gas separator 50 to which effluent gas from thefluidized bed reactor 30 is introduced, the effluent gas separator 50separating hydrogen from trichlorosilane and silicon tetrachloride. Aconveying apparatus conveys trichlorosilane and silicon tetrachloridefrom the effluent gas separator 50 to the purification system 4.

The system includes a hydrogenated gas separator 70 to whichhydrogenated gas from the hydrogenation reactor is introduced. Thehydrogenated gas separator 70 separates trichlorosilane and unreactedsilicon tetrachloride from hydrogen and unreacted hydrogen chloride. Aconveying apparatus conveys trichlorosilane and unreacted silicontetrachloride to the purification system 4.

The system may also include a separation system 52 to which hydrogen andhydrogen chloride from the hydrogenated gas separator are introduced toseparate hydrogen and hydrogen chloride. A conveying apparatus conveyshydrogen chloride from the separation system 52 to the chlorinationreactor 7. A conveying apparatus conveys hydrogen from the separationsystem 52 to at least one of the fluidized bed reactor 30 andhydrogenation reactor 60.

A system for producing polycrystalline silicon according to a secondembodiment of the present disclosure is shown in FIG. 2. The system issimilar to the system of FIG. 1; however, the system of FIG. 2 includesa second fluidized bed reactor 180 in which silicon is added to producetrichlorosilane according to reaction (8) above. The system includes achlorination reactor 107 in which hydrogen chloride is contacted withsilicon to produce trichlorosilane and silicon tetrachloride. The systemalso includes a first fluidized bed reactor 130 in which trichlorosilaneis decomposed to produce polycrystalline silicon and a second fluidizedbed reactor 180 in which silicon tetrachloride is converted totrichlorosilane. A conveying apparatus conveys trichlorosilane from thechlorination reactor 107 to the first fluidized bed reactor 130.

The system includes a purification system 104 to which trichlorosilaneand silicon tetrachloride are introduced to separate trichlorosilane andsilicon tetrachloride. A conveying apparatus conveys trichlorosilanefrom the purification system 104 to the first fluidized bed reactor 130and a conveying apparatus conveys silicon tetrachloride from thepurification system 104 to the second fluidized bed reactor 180.

The system may include a first effluent gas separator 150 to whicheffluent gas from the first fluidized bed reactor 130 is introduced. Theeffluent gas separator 150 separates hydrogen from trichlorosilane andsilicon tetrachloride. A conveying apparatus conveys trichlorosilane andsilicon tetrachloride from the first effluent gas separator 150 to thepurification system 104.

The system includes a second effluent gas separator system 190 to whicha second effluent gas from the second fluidized bed reactor 180 isintroduced. The second effluent gas separator 190 separatestrichlorosilane and unreacted silicon tetrachloride from unreactedhydrogen. A conveying apparatus conveys trichlorosilane and unreactedsilicon tetrachloride to the purification system 104.

The system according to the second embodiment of the present disclosuremay also include a separation system 152 to which hydrogen and hydrogenchloride from the second effluent gas separator 190 are introduced toseparate hydrogen and hydrogen chloride. A conveying apparatus conveyshydrogen chloride from the separation system 152 to the chlorinationreactor 107 and a conveying apparatus conveys hydrogen from theseparation system 152 to at least one of the first fluidized bed reactor107 and the second fluidized bed reactor 180.

In this regard, suitable conveying apparatus for use in the systems ofFIG. 1 and FIG. 2 are conventional and well known in the art. Suitableconveying apparatus for the transfer of gases include, for example, arecirculation fan or blower and suitable conveying apparatus fortransfer of solids include, for example, drag, screw, belt and pneumaticconveyors. In this regard, it should be understood that, use of thephrase “conveying apparatus” herein is not meant to imply directtransfer from one unit of the system to another but rather only that thematerial is transferred from one unit to another by any number ofindirect transfer parts and/or mechanisms. For instance, material fromone unit may be conveyed to further processing units (e.g.,purification) and then conveyed to the second unit. In this example,each unit of conveyance including the intermediate processing equipmentitself may be considered to be the “conveying apparatus” and the phrase“conveying apparatus” should not be considered in a limiting sense.

Preferably, all equipment utilized in the systems for producingpolycrystalline silicon is resistant to corrosion in an environment thatincludes exposure to compounds used and produced within the system.Suitable materials of construction are conventional and well-known inthe field of the invention and include, for example, carbon steel,stainless steel, MONEL alloys, INCONEL alloys, HASTELLOY alloys, nickel,graphite (e.g., extruded or iso-molded) and silicon carbide (e.g.,converted graphite or extruded).

As shown in FIG. 1 and in FIG. 2, the systems and processes aresubstantially closed loop with respect to hydrogen, hydrogen chlorideand trichlorosilane in that the system does not include hydrogen,hydrogen chloride or trichlorosilane in the inlet stream 3 (and instreams 103, 185 as in FIG. 2) and these compounds are not removed fromthe system in outlet stream 27 (or 127 as in FIG. 2). In this regard, itshould be understood that amounts of hydrogen, hydrogen chloride ortrichlorosilane may be removed from the system in a purge stream and maybe fed into the system or process as in a make-up stream. Make-up ofthese compounds may be achieved by addition of the compounds to anyprocess stream as may be determined by those of skill in the art.

It should be understood that the processes and systems described abovemay include more than one of any of the recited units (e.g., reactorsand/or separation units) and that multiple units may be operated inseries and/or in parallel without departing from the scope of thepresent disclosure. Further in this regard, it should be understood thatthe process and systems that are described are exemplary and theprocesses and systems may include additional units which carryadditional functions without limitation.

When introducing elements of the present disclosure or the preferredembodiments(s) thereof, the articles “a”, “an”, “the” and “said” areintended to mean that there are one or more of the elements. The terms“comprising”, “including” and “having” are intended to be inclusive andmean that there may be additional elements other than the listedelements.

As various changes could be made in the above apparatus and methodswithout departing from the scope of the disclosure, it is intended thatall matter contained in the above description and shown in theaccompanying figures shall be interpreted as illustrative and not in alimiting sense.

What is claimed is:
 1. A system for producing polycrystalline silicon bydecomposition of trichlorosilane, the system being substantiallyclosed-loop with respect to trichlorosilane, the system comprising: achlorination reactor in which hydrogen chloride is contacted withsilicon to produce trichlorosilane and silicon tetrachloride; afluidized bed reactor in which trichlorosilane is decomposed to producepolycrystalline silicon; and a hydrogenation reactor in which silicontetrachloride and hydrogen are introduced without silicon to producetrichlorosilane.
 2. The system as set forth in claim 1 comprising: aconveying apparatus for conveying trichlorosilane from the hydrogenationreactor to the fluidized bed reactor; and a conveying apparatus forconveying trichlorosilane from the chlorination reactor to the fluidizedbed reactor.
 3. The system as set forth in claim 1 comprising apurification system to which trichlorosilane and silicon tetrachlorideare introduced to separate trichlorosilane and silicon tetrachloride. 4.The system as set forth in claim 3 comprising: a conveying apparatus forconveying trichlorosilane from the purification system to the fluidizedbed reactor; and a conveying apparatus for conveying silicontetrachloride from the purification system to the hydrogenation reactor.5. The system as set forth in claim 3 comprising an effluent gasseparator to which effluent gas from the fluidized bed reactor isintroduced, the effluent gas comprising silicon tetrachloride, hydrogenand unreacted trichlorosilane, wherein the effluent gas separatorseparates hydrogen from trichlorosilane and silicon tetrachloride. 6.The system as set forth in claim 5 comprising a conveying apparatus forconveying trichlorosilane and silicon tetrachloride from the effluentgas separator to the purification system.
 7. The system as set forth inclaim 3 comprising a hydrogenated gas separator to which hydrogenatedgas from the hydrogenation reactor is introduced, the hydrogenated gascomprising trichlorosilane, hydrogen chloride, unreacted hydrogen andunreacted silicon tetrachloride, wherein the hydrogenated gas separatorseparates trichlorosilane and unreacted silicon tetrachloride fromhydrogen and unreacted hydrogen chloride.
 8. The system as set forth inclaim 7 comprising a conveying apparatus for conveying trichlorosilaneand unreacted silicon tetrachloride to the purification system.
 9. Thesystem as set forth in claim 7 comprising a separation system to whichhydrogen and hydrogen chloride from the hydrogenated gas separator areintroduced to separate hydrogen and hydrogen chloride.
 10. The system asset forth in claim 9 comprising: a conveying apparatus for conveyinghydrogen chloride from the separation system to the chlorinationreactor; and a conveying apparatus for conveying hydrogen from theseparation system to at least one of the fluidized bed reactor and thehydrogenation reactor.
 11. A system for producing polycrystallinesilicon by decomposition of trichlorosilane, the system beingsubstantially closed-loop with respect to trichlorosilane, the systemcomprising: a chlorination reactor in which hydrogen chloride iscontacted with silicon to produce trichlorosilane and silicontetrachloride; a first fluidized bed reactor in which trichlorosilane isdecomposed to produce polycrystalline silicon; and a second fluidizedbed reactor in which silicon tetrachloride is contacted with hydrogenand particulate silicon to produce trichlorosilane.
 12. The system asset forth in claim 11 comprising a conveying apparatus for conveyingtrichlorosilane from the chlorination reactor to the first fluidized bedreactor.
 13. The system as set forth in claim 11 comprising apurification system to which trichlorosilane and silicon tetrachlorideare introduced to separate trichlorosilane and silicon tetrachloride.14. The system as set forth in claim 13 comprising: a conveyingapparatus for conveying trichlorosilane from the purification system tothe first fluidized bed reactor; and a conveying apparatus for conveyingsilicon tetrachloride from the purification system to the secondfluidized bed reactor.
 15. The system as set forth in claim 13comprising a first effluent gas separator to which effluent gas from thefirst fluidized bed reactor is introduced, the effluent gas comprisingsilicon tetrachloride, hydrogen and unreacted trichlorosilane, whereinthe first effluent gas separator separates hydrogen from trichlorosilaneand silicon tetrachloride.
 16. The system as set forth in claim 15comprising a conveying apparatus for conveying trichlorosilane andsilicon tetrachloride from the first effluent gas separator to thepurification system.
 17. The system as set forth in claim 13 comprisinga second effluent gas separator system to which a second effluent gasfrom the second fluidized bed reactor is introduced, the second effluentgas comprising trichlorosilane, unreacted trichlorosilane and unreactedhydrogen, wherein the second effluent gas separator separatestrichlorosilane and unreacted silicon tetrachloride from unreactedhydrogen.
 18. The system as set forth in claim 17 comprising a conveyingapparatus for conveying trichlorosilane and unreacted silicontetrachloride to the purification system.
 19. The system as set forth inclaim 17 comprising a separation system to which hydrogen and hydrogenchloride from the second effluent gas separator are introduced toseparate hydrogen and hydrogen chloride.
 20. The system as set forth inclaim 19 comprising: a conveying apparatus for conveying hydrogenchloride from the separation system to the chlorination reactor; and aconveying apparatus for conveying hydrogen from the separation system toat least one of the first fluidized bed reactor and the second fluidizedbed reactor.
 21. The system as set forth in claim 11 wherein thechlorination reactor is a fluidized bed reactor.